Characterization of Poly(N-
(hydroxymethyl)methacrylamide-ATU) Hydrogels
Synthesized by Radiation
Nurettin S ¸ ahiner,
1
O
¨
mu ¨rC ¸ elikbıc ¸ak,
1
Savas ¸ Malcı,
1
O
¨
mer Kantog ˇ lu,
2
Bekir Salih
1
1
Department of Chemistry, Hacettepe University, 06532 Ankara, Turkey
2
Ankara Nuclear Research Center, Turkish Atomic Energy Authority, 06983 Ankara, Turkey
Received 18 February 2005; accepted 19 June 2005
DOI 10.1002/app.22462
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: Poly(N-(hydroxymethyl)methacrylamide-1-
allyl-2-thiourea), (poly(NHMMA-ATU)) hydrogels were
synthesized by radiation, using
60
Co source at different
radiation doses, to change the porosity and crosslinking
density of the hydrogels. The percent of 1-allyl-2-thiourea
(ATU) in the monomer mixture before the irradiation was
varied between 2.5% and 10.0%, to increase the content of
ATU, which was involved in some different applications in
the hydrogels. Fourier transform infrared spectroscopy
(FTIR), thermogravimetric analysis (TGA), elemental analy-
sis, and the swelling experiments were used to characterize
the poly(NHMMA-ATU) hydrogels synthesized in this
study. Characterization results of hydrogels showed that
crosslinking density of the hydrogels was increased by the
increasing radiation dose and ATU content in the irradiated
mixture. Swellability of these hydrogels was found to be
high enough to allow the metal ions and biomolecules get-
ting inside the hydrogels to interact with all active groups
on/in the hydrogels in the adsorption applications. Equilib-
rium swelling ratio of the hydrogels at pH 0.5 is at least half
of the equilibrium swelling ratio of the hydrogels at pH 7.0.
Oscillatory swelling behavior of poly(NHMMA-ATU) hy-
drogels between pH 0.5 and pH 7.0 showed that the hydro-
gels are quite stable at different pH conditions. © 2005 Wiley
Periodicals, Inc. J Appl Polym Sci 99: 1657–1664, 2006
Key words: N-(hydroxymethyl)methacrylamide; 1-allyl-2-
thiourea; hydrogels; irradiation; swelling
INTRODUCTION
Chelating polymeric ligands have been extensively
studied by several authors and many reviews are
available in the field.
1–3
Recently, a great deal of inter-
est has been observed in relation to the applicability of
chelating agents for removal and separation of metal
ions from heavy metal contaminated water and pre-
concentration of precious metal ions from different
samples.
4–6
Among many sorptive materials, various
forms of synthetic polymers containing complexing
molecules which are available at low cost have
emerged as one of the most important matrices for the
synthesis of new sorbents.
7–9
In the recent years, in-
stead of chelating resins, some hydrogels having dif-
ferent swelling ratio have been used for different ap-
plications.
10,11
Hydrogels are special class of crosslinked
polymers, and they can be prepared by different po-
lymerization techniques. Using radiation technology,
the polymerization procedure, the crosslinking struc-
ture, and also the crosslinking density of the hydro-
gels could be controlled easily.
12
Hydrogels are poly-
meric networks, which absorb and retain large
amounts of water. Hydrogels having different ioniz-
able and hydrogen bonding capacity, show different
swelling behavior in the solution at different pH, tem-
perature, and ionic strength. These behaviors supply
some advantages to the hydrogels in different appli-
cations, especially in drug delivery systems.
13–15
Be-
cause of their water-absorbing capacity, hydrogels are
subject of investigation of researchers interested in
fundamental aspects of swollen polymeric networks,
and have also found widespread application in differ-
ent technological areas, such as materials for contact
lenses and protein separation, matrices for cell encap-
sulation, removal of metal ions, adsorption of textile
dyes, and devices for the controlled release of drugs
and proteins.
16 –21
The advantages of the hydrogels are
easy to obtain with some different polymerization
techniques, and interacting species with the active
functional group on/in to the polymeric sorbent could
be penetrated inside cavities of hydrogel by the
swellability of the hydrogels. Recently, there has
been a substantial interest in the use of radiation-
induced graft copolymerization of functionalized
monomer onto polymeric hydrogels, for chelating
sorbent materials.
22–25
In the present study, poly(N-
(hydroxymethyl)methacrylamide-1-allyl-2-thio-
Correspondence to: B. Salih (bekir@hacettepe.edu.br).
Contract grant sponsor: Hacettepe University Scientific Re-
search Foundation; contract grant number: HU 0302601007.
Journal of Applied Polymer Science, Vol. 99, 1657–1664 (2006)
© 2005 Wiley Periodicals, Inc.